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在气溶表面促进有机酸的CO2反应

  • 0State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China.

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Reactions of Carboxylic Acids: Introduction 01:41

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Carboxylic acids possess an acidic –COOH functional group. The acidity can be attributed to the resonance stabilization of their conjugate base, wherein the negative charge is delocalized over both oxygen atoms.

The acyl bond is polar because of the high electronegativity of oxygen, making the carbonyl carbon highly reactive and susceptible to nucleophilic attack. Thus, nucleophilic acyl substitution reactions can convert the –COOH to acid derivatives such as acyl halides, esters,...

Carboxylic Acids to Acid Chlorides 01:18

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Carboxylic acids react with SOCl2 or PCl5 to form acid chlorides. Amongst the carboxylic acid derivatives, acid chlorides are the most reactive and synthetically important derivatives. They are useful reagents for Friedel–Crafts acylation of some aromatic compounds.

An alternative reagent for converting a carboxylic acid to an acid chloride is phosphorus pentachloride. The mechanism involves the attack by a carboxylic acid at the phosphorus center of PCl5 while eliminating a chloride ion....

Relative Reactivity of Carboxylic Acid Derivatives 01:13

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Carboxylic acid derivatives such as acid halides, anhydrides, esters, and amides undergo nucleophilic acyl substitution reactions with varying degrees of reactivity.
A key factor in assessing the reactivity of the acid derivatives is the basicity of the substituent or the leaving group. The lower the basicity of the leaving group, the higher the reactivity of the derivative. The basicity of the leaving group follows this order:
Halide ions < Acyloxy ions < Alkoxy ions < Amine ions

Loss of Carboxy Group as CO<sub data-lazy-src=

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Carboxylic acids, upon heating, undergo a decarboxylation reaction by releasing carbon dioxide gas. Monocarboxylic acids do not undergo decarboxylation easily. However, a silver salt of carboxylic acid reacts with bromine or iodine under high temperature to release carbon dioxide gas and forms halide with one less carbon. This reaction is called the Hunsdiecker reaction.

Unlike monocarboxylic acids, ꞵ-keto acids bearing a keto group at the β position to the carboxyl group, readily undergo...

Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents 01:13

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Carboxylic acids can be prepared by the carboxylation of Grignard reagents (RMgX). This method is convenient for converting alkyl (primary, secondary or tertiary), vinyl, benzyl, and aryl halides to carboxylic acids with one additional carbon than the starting RMgX.

The carboxylation mechanism involves two steps. In the first step, the nucleophilic attack of the Grignard reagent on the electrophilic site of the carbon dioxide generates the magnesium salt of the carboxylate ion. In the...

Acid Halides to Carboxylic Acids: Hydrolysis 01:01

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Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic...